JP2003221442A - Metal cluster-containing phenylazomethine dendrimer - Google Patents
Metal cluster-containing phenylazomethine dendrimerInfo
- Publication number
- JP2003221442A JP2003221442A JP2002020785A JP2002020785A JP2003221442A JP 2003221442 A JP2003221442 A JP 2003221442A JP 2002020785 A JP2002020785 A JP 2002020785A JP 2002020785 A JP2002020785 A JP 2002020785A JP 2003221442 A JP2003221442 A JP 2003221442A
- Authority
- JP
- Japan
- Prior art keywords
- metal cluster
- phenylazomethine dendrimer
- metal
- dendrimer
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000412 dendrimer Substances 0.000 title claims abstract description 51
- 229920000736 dendritic polymer Polymers 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 claims abstract description 16
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims description 13
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- -1 biphenyloxy groups Chemical group 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 101100484954 Arabidopsis thaliana VQ20 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000003884 phenylalkyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この出願の発明は、金属クラ
スター内包フェニルアゾメチンデンドリマーに関するも
のである。さらに詳しくは、この出願の発明は、発光材
料をはじめ、電子材料、触媒等として有用な、フェニル
アゾメチンデンドリマー内における金属クラスター形成
による新しい錯体物質と、その発光機能を利用した発光
材料に関するものである。TECHNICAL FIELD The present invention relates to a metal cluster-encapsulating phenylazomethine dendrimer. More specifically, the invention of this application relates to a novel complex substance, which is useful as a light emitting material, an electronic material, a catalyst, etc., by forming a metal cluster in a phenylazomethine dendrimer, and a light emitting material utilizing the light emitting function. .
【０００２】[0002]
【従来の技術とその課題】近年、ディスプレイやノート
型パソコンの高性能化に伴い、従来にない高分子錯体材
料を用いた高精度発光材料の開発と実用化が望まれてい
る。2. Description of the Related Art In recent years, with the improvement in performance of displays and notebook personal computers, there has been a demand for the development and practical application of high-precision light emitting materials using polymer complex materials that have never existed before.
【０００３】従来の発光材料は、主にバルクな金属・無
機物質から構成されているが、最近では、より高い発光
輝度や発光波長の精密なコントロールが可能な金属クラ
スターの発光特性が注目を集めている。Conventional light-emitting materials are mainly composed of bulk metal / inorganic substances, but recently, the light-emitting characteristics of metal clusters capable of higher emission brightness and precise control of emission wavelength have attracted attention. ing.
【０００４】このような金属クラスターを用いた発光に
おいては、構成金属原子数とクラスター構造の制御が不
可欠であるが、金属イオンのバルク還元等による手法で
は生成した金属クラスター同士の凝集のため均一な金属
クラスターの合成はこれまで困難であった。In light emission using such metal clusters, it is essential to control the number of constituent metal atoms and the cluster structure. However, in the method such as bulk reduction of metal ions, the generated metal clusters are agglomerated with each other, so that they are uniform. The synthesis of metal clusters has been difficult until now.
【０００５】一方、フェニルアゾメチンデンドリマーは
金属塩に対し高い配位性をもつアゾメチン部位を多数有
しており、また、電子勾配によりデンドリマー内の金属
塩の数と位置を精密にコントロールできることが期待さ
れる。On the other hand, phenylazomethine dendrimers have a large number of azomethine moieties having high coordination with metal salts, and it is expected that the number and position of metal salts in dendrimers can be precisely controlled by electron gradient. It
【０００６】デンドリマーのようにある程度閉鎖された
空間内に発光機能を有する金属クラスターを包接できれ
ば、クラスター同士の凝集および衝突による消光が抑え
られ高輝度発光が実現されると考えられるからである。It is considered that if a metal cluster having a light emitting function can be included in a space which is closed to some extent like a dendrimer, quenching due to agglomeration and collision of the clusters can be suppressed and high brightness light emission can be realized.
【０００７】しかしながら、フェニルアゾメチンデンド
リマーを用いた金属クラスター包接物質はこれまで提供
されていないのが実情である。However, the fact is that no metal cluster inclusion material using a phenylazomethine dendrimer has been provided so far.
【０００８】そこで、この出願の発明は、以上の通りの
事情に鑑みてなされたものであり、従来のバルク金属発
光材料に代わるもの、あるいは新しい電子材料や触媒等
としてその有用性が期待される、新規な金属クラスター
内包のフェニルアゾメチンデンドリマーとこれを用いた
発光材料を提供することを課題としている。Therefore, the invention of this application has been made in view of the circumstances as described above, and is expected to be useful as an alternative to the conventional bulk metal light emitting material, or as a new electronic material or catalyst. , And to provide a novel phenylazomethine dendrimer containing a metal cluster and a luminescent material using the same.
【０００９】[0009]
【課題を解決するための手段】この出願の発明は、上記
の課題を解決するものとして、第１には、分子樹状構造
を有するフェニルアゾメチンデンドリマーに金属クラス
ターが内包されている錯体物質であって、次の一般式Means for Solving the Problems The invention of this application is to solve the above-mentioned problems. Firstly, a phenylazomethine dendrimer having a molecular dendritic structure is a complex substance containing a metal cluster. And the following general formula
【００１０】[0010]
【化５】 [Chemical 5]
【００１１】（式中のＡは、フェニルアゾメチンデンド
リマーの中核分子基であり、次式(A in the formula is a core molecular group of phenylazomethine dendrimer, and is represented by the following formula:
【００１２】[0012]
【化６】 [Chemical 6]
【００１３】の構造で表され、Ｒ1は、置換基を有して
いてもよい芳香族基を示し、ｌはＲ1への結合数を示
し；Ｂは、前記Ａに対してｌ個のアゾメチン結合を形成
する次式R 1 represents an aromatic group which may have a substituent, l represents the number of bonds to R 1 , and B represents 1 of the above A. The following formula for forming an azomethine bond
【００１４】[0014]
【化７】 [Chemical 7]
【００１５】の構造で表わされ、Ｒ2は、同一または別
異に置換基を有していてもよい芳香族基を示し；Ｒは、
末端基として前記Ｂにアゾメチン結合する次式R 2 is an aromatic group which may be the same or different and which may have a substituent; R is
The following formula for azomethine bond to B as an end group
【００１６】[0016]
【化８】 [Chemical 8]
【００１７】の構造で表わされ、Ｒ3は、同一または別
異に置換基を有していてもよい芳香族基を示し；ｎは、
フェニルアゾメチンデンドリマーの前記Ｂの構造を介し
ての世代数を示し；ｍは、フェニルアゾメチンデンドリ
マーの末端基Ｒの数を表し、ｎ＝０の時はｍ＝ｌであ
り、ｎ≧１の時は、ｍ＝２ｎｌであり；Ｄは金属クラス
ターを、ｋは金属クラスターＤの数を各々表わしてい
る）で示されることを特徴とする金属クラスター内包フ
ェニルアゾメチンデンドリマーを提供する。R 3 represents the same or different aromatic group which may have a substituent; and n represents
The number of generations of the phenylazomethine dendrimer through the structure of B is shown; m represents the number of terminal groups R of the phenylazomethine dendrimer, m = 1 when n = 0, and n ≧ 1. , M = 2nl; D represents a metal cluster, and k represents the number of the metal cluster D), thereby providing a phenylazomethine dendrimer containing a metal cluster.
【００１８】また、第２には、金属クラスター（Ｄ）
は、半導体金属原子またはそのイオンのクラスターであ
ることを特徴とする前記の金属クラスター内包フェニル
アゾメチンデンドリマーを提供する。Secondly, the metal cluster (D)
Provides a phenylazomethine dendrimer containing a metal cluster, which is a cluster of a semiconductor metal atom or an ion thereof.
【００１９】そして、この出願の発明は、第３には、前
記第２の発明の金属クラスター内包フェニルアゾメチン
デンドリマーを含有することを特徴とする発光材料を提
供する。Thirdly, the invention of this application provides a light-emitting material containing the phenylazomethine dendrimer containing a metal cluster of the second invention.
【００２０】以上のとおりのこの出願の発明は、前記の
課題を解決すべく、発明者が鋭意研究を重ねた結果、フ
ェニルアゾメチンデンドリマーと錯形成した金属イオン
を化学的あるいは電気化学的に酸化還元することによっ
てデンドリマー内に均一な金属クラスターを生成させる
ことができるとの知見に基づいている。そして、さら
に、この金属クラスター内包デンドリマーの発光特性を
発光材料へと応用することで、この出願の発明が完成さ
れている。In order to solve the above-mentioned problems, the invention of this application as described above has been earnestly studied by the inventor, and as a result, the metal ion complexed with phenylazomethine dendrimer was chemically or electrochemically redox-reduced. It is based on the finding that uniform metal clusters can be generated in the dendrimer. Then, the invention of this application has been completed by further applying the luminescent property of the metal cluster-containing dendrimer to a luminescent material.
【００２１】この出願の発明の金属クラスター内包フェ
ニルアゾメチンデンドリマーでは、最初に錯形成させる
金属イオンの種類と数を変えることでクラスターのサイ
ズと個数を自在にコントロールすることが可能であるた
め、従来の発光材料と異なり、多様かつ波長幅の極めて
小さい高輝度発光特性の発現が可能となる。In the metal cluster-containing phenylazomethine dendrimer of the invention of the present application, the size and number of clusters can be freely controlled by changing the type and number of metal ions to be complexed first, and thus it is possible to reduce Different from the light emitting material, it is possible to exhibit various high brightness light emitting characteristics having a very narrow wavelength width.
【００２２】[0022]
【発明の実施の形態】この出願の発明は以上のとおりの
特徴をもつものであるが、以下にその実施の形態につい
て説明する。BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application has the characteristics as described above, and the embodiments thereof will be described below.
【００２３】前記のとおりの一般式で表わされるこの出
願の発明の錯体物質においては、これを構成するフェニ
ルアゾメチンデンドリマーの符号Ｒ1、Ｒ2およびＲ3で
示される置換基を有していてもよい芳香族基は、その骨
格構造として、フェニル基またはその類縁の構造であっ
てよく、たとえば、フェニル基、ビフェニル基、ビフェ
ニルアルキレン基、ビフェニルオキシ基、ビフェニルカ
ルボニル基、フェニルアルキル基等の各種のものが例示
され、これらは、置換基として、塩素原子、臭素原子、
フッ素原子等のハロゲン原子、メチル基、エチル基等の
アルキル基、クロルメチル基、トリフルオロメチル基等
のハロゲンアルキル基、メトキシ基、エトキシ基等のア
ルコキシ基、メトキシエチル基等のアルコキシアルキル
基、アルキルチオ基、カルボニル基、シアノ基、アミノ
基、ニトロ基等の各種の置換基を１ないし２以上、また
適宜に複数種のものとして有していてもよい。In the complex substance of the invention of this application represented by the general formula as described above, even if it has a substituent represented by the symbols R 1 , R 2 and R 3 of the phenylazomethine dendrimer constituting the complex substance A good aromatic group may have a phenyl group or a structure related thereto as a skeleton structure, and examples thereof include various phenyl groups, biphenyl groups, biphenylalkylene groups, biphenyloxy groups, biphenylcarbonyl groups, phenylalkyl groups and the like. Examples of these, as these substituents, chlorine atom, bromine atom,
Halogen atom such as fluorine atom, alkyl group such as methyl group and ethyl group, halogen alkyl group such as chloromethyl group and trifluoromethyl group, alkoxy group such as methoxy group and ethoxy group, alkoxyalkyl group such as methoxyethyl group, alkylthio It may have 1 to 2 or more of various substituents such as a group, a carbonyl group, a cyano group, an amino group, and a nitro group, and may appropriately have plural kinds of substituents.
【００２４】なかでも、メトキシ基、アミノ基のような
電子供与位の高い官能基あるいはシアノ基やカルボニル
基のような電子受容性の高い官能基が望ましい。Of these, a functional group having a high electron donating position such as a methoxy group or an amino group or a functional group having a high electron accepting property such as a cyano group or a carbonyl group is preferable.
【００２５】前記式Ｒ1（−Ｎ＝）ｌの中核部分におい
て、数ｌは、特に限定されることはないが、１以上の数
であって、たとえば１〜４の場合のものが例示される。In the core part of the above formula R 1 (-N =) l, the number l is not particularly limited, but is a number of 1 or more, for example 1 to 4 is exemplified. It
【００２６】デンドリマーの世代数（ｎ）については、
０または１以上であるが、たとえば３〜５世代のものが
発光材料への応用等の観点からは好ましいものとして例
示される。Regarding the number of generations (n) of dendrimers,
It is 0 or 1 or more, but those of the 3rd to 5th generations are exemplified as preferable from the viewpoint of application to light emitting materials and the like.
【００２７】金属クラスター（Ｄ）は、各種の金属原子
またはそのイオンによって構成されてよく、なかでも発
光材料や電子材料への応用の観点からは、Ｓｎ、Ｇａ、
Ｔｉ、Ｉｎ、Ｇｅ、Ｔａ、Ｚｒ、Ｈｆ、Ｓｂ、Ｓｉ、
Ｂ、Ｍｎ、Ｆｅ、Ｖ、Ｍｏ、Ｗ、Ｐｂ、Ｚｎ、Ｃｄ、Ｃ
ｕ、Ｎｉ、Ｙ、Ｓｃ、Ｅｕ、Ｅｒ、Ｌａ等が好ましいも
のとして例示され、さらには半導体金属原子またはその
イオンが挙げられる。The metal cluster (D) may be composed of various metal atoms or ions thereof, and from the viewpoint of application to light emitting materials and electronic materials, Sn, Ga,
Ti, In, Ge, Ta, Zr, Hf, Sb, Si,
B, Mn, Fe, V, Mo, W, Pb, Zn, Cd, C
u, Ni, Y, Sc, Eu, Er, La and the like are exemplified as preferable ones, and further, a semiconductor metal atom or its ion is mentioned.
【００２８】これらの金属は、イオンとして酸素イオン
等の対イオンを有するものとしてクラスターを構成して
もよい。These metals may form a cluster by having counter ions such as oxygen ions as ions.
【００２９】一般式として前記のとおりに表わされるデ
ンドリマーについては公知の方法をはじめとして各種の
方法で合成することができる。たとえば、四塩化チタン
や、パラトルエンスルホン酸などの酸存在下で、ジアミ
ノベンゾフェノンの脱水反応によってデンドリマーの世
代数（ｎ）を増やしていくことができる。The dendrimer represented by the general formula as described above can be synthesized by various methods including known methods. For example, the generation number (n) of dendrimers can be increased by dehydration reaction of diaminobenzophenone in the presence of an acid such as titanium tetrachloride or paratoluenesulfonic acid.
【００３０】また、この出願の発明の金属クラスター内
包のデンドリマー錯体の合成については、前記各種の方
法により合成されたフェニルアゾメチンデンドリマー
に、金属化合物を混合することで、配位錯体を生成させ
ることで可能とされる。Regarding the synthesis of the metal cluster-encapsulating dendrimer complex of the invention of this application, a coordination complex is formed by mixing a metal compound with the phenylazomethine dendrimer synthesized by the various methods described above. Made possible.
【００３１】この場合、配位数については、デンドリマ
ーのアゾメチン結合の総数の範囲内において、所定モル
数の金属化合物の混合によって調整が可能とされる。こ
の配位に際して特徴的なことは、金属原子またはイオン
が、デンドリマーの樹状分子構造において中心から外側
へと段階的に、添加する金属化合物のモル数に対応して
規則正しく錯位集積されるという特異的な挙動が見られ
ることである。このような挙動は分子の中の電子勾配に
基づくものと考えられ、この電子勾配は、中心や外側の
部分構造（置換基）を変えることで簡単に変化させるこ
とができる。In this case, the coordination number can be adjusted by mixing a predetermined number of moles of the metal compound within the range of the total number of azomethine bonds of the dendrimer. A characteristic of this coordination is that metal atoms or ions are complexed in a regular manner in the dendritic molecular structure of the dendrimer from the center to the outside in a stepwise manner corresponding to the number of moles of the metal compound added. Behavior is seen. Such behavior is considered to be based on the electron gradient in the molecule, and this electron gradient can be easily changed by changing the central or outer partial structure (substituent).
【００３２】デンドリマーへの配位については、溶媒を
用いることができる。なかでも、ハロゲン化炭化水素、
ニトリル類、アミド類などの極性溶媒が好ましく、たと
えば塩化メチレン、アセトニトリル、ＤＭＦ、ＤＭＳＯ
等が例示される。配位のための混合は、温度としては、
−１０℃〜３０℃程度でよく、雰囲気は大気中、あるい
はＡｒ、Ｎ2等の不活性雰囲気とすることができる。For coordination to the dendrimer, a solvent can be used. Among them, halogenated hydrocarbons,
Polar solvents such as nitriles and amides are preferable, for example, methylene chloride, acetonitrile, DMF, DMSO.
Etc. are illustrated. Mixing for coordination, as temperature
The temperature may be about −10 ° C. to 30 ° C., and the atmosphere may be the air or an inert atmosphere such as Ar or N 2 .
【００３３】得られた配位錯体については、錯形成した
金属イオンを化学的あるいは電気化学的に酸化還元する
ことによって、デンドリマー分子内に均一な金属クラス
ターを生成させることができる。これによって、錯体物
質としての金属クラスター内包のフェニルアゾメチンデ
ンドリマーが得られる。With respect to the obtained coordination complex, a uniform metal cluster can be formed in the dendrimer molecule by subjecting the complexed metal ion to redox chemically or electrochemically. As a result, a phenylazomethine dendrimer containing a metal cluster as a complex substance is obtained.
【００３４】化学的な酸化還元は、各種の酸化剤や還元
剤を用いることで可能とされる。たとえば酸化剤として
はベンゾキノンなどが代表的なものとして挙げられる。
上記の金属イオン配位錯体の生成に続いてこれらの酸化
還元を行うことができる。Chemical redox can be performed by using various oxidizing agents and reducing agents. For example, benzoquinone is a typical example of the oxidizing agent.
These oxidation-reduction can be performed subsequent to the formation of the above-mentioned metal ion coordination complex.
【００３５】このような酸化還元においては、内包した
金属イオンの酸化還元電位を考慮して、酸化剤や還元
剤、そして電界電位を選択すればよい。In such redox, the oxidizing agent, the reducing agent, and the electric field potential may be selected in consideration of the redox potential of the encapsulated metal ions.
【００３６】そこで以下に実施例を示し、さらに詳しく
説明する。Therefore, an embodiment will be shown below and further detailed description will be given.
【００３７】もちろん、以下の例によって発明が限定さ
れることはない。Of course, the invention is not limited to the following examples.
【００３８】[0038]
【実施例】＜実施例１＞金属クラスター内包フェニルア
ゾメチンデンドリマーの合成
次の反応式に従って、金属としてのＳｎのクラスター内
包フェニルアゾメチンデンドリマーを合成した。EXAMPLES Example 1 Synthesis of Metal Cluster-Encapsulated Phenylazomethine Dendrimer A cluster-encapsulated phenylazomethine dendrimer of Sn as a metal was synthesized according to the following reaction formula.
【００３９】[0039]
【化９】 [Chemical 9]
【００４０】すなわち、まず、ベンゾフェノンとジアミ
ノベンゾフェノンを、クロルベンゼン溶媒中において、
ＴｉＣｌ4、ＤＡＢＣ０の存在下に１００℃の温度で反
応させ、さらに順次にジアミノベンゾフェノンと反応さ
せて次代数を増加させた後にジアミノベンゼンと反応さ
せるか、あるいはこの反応の追種を逆にたどることによ
って、式に示した前記フェニルアゾメリンデンドリマー
を合成し、次いで、このフェニルアゾメチンデンドリマ
ーの塩化メチレン／アセトニトリル溶液に、塩化スズの
アセトニトリル溶液を添加することによって、塩化スズ
がデンドリマーあたり３０個配位した錯体が得られた。
得られたデンドリマー錯体をベンゾキノンによって酸化
すると、酸化スズのクラスターの生成に基づく６３０ｎ
ｍの発光が観測された。That is, first, benzophenone and diaminobenzophenone are added in a chlorobenzene solvent,
Reaction in the presence of TiCl 4 or DABC0 at a temperature of 100 ° C., further reaction with diaminobenzophenone in order to increase the next algebra, and then reaction with diaminobenzene, or tracing of this reaction in reverse. By synthesizing the phenylazomethine dendrimer represented by the formula, and then adding tin chloride in acetonitrile solution to the phenylazomethine dendrimer in methylene chloride / acetonitrile solution to coordinate 30 tin chlorides per dendrimer. A complex was obtained.
Oxidation of the resulting dendrimer complex with benzoquinone yielded 630n based on the formation of tin oxide clusters.
Luminescence of m was observed.
【００４１】得られた錯体は、表１のとおり、原子吸光
スペクトル、赤外吸収スペクトル、およびマススペクト
ルにより同定した。The obtained complex was identified by atomic absorption spectrum, infrared absorption spectrum and mass spectrum as shown in Table 1.
【００４２】[0042]
【表１】 [Table 1]
【００４３】＜実施例２＞クラスターサイズに基づく発
光波長のコントロール
デンドリマーに対し、１４等量の塩化スズと錯形成さ
せ、実施例１と同様にベンゾキノンにより酸化させたと
ころ、５１０ｎｍの発光が観測された。デンドリマー内
のクラスターサイズを変えることで、発光は単波長へと
シフトした。Example 2 A control dendrimer having an emission wavelength based on the cluster size was complexed with 14 equivalents of tin chloride and oxidized with benzoquinone in the same manner as in Example 1, and emission of 510 nm was observed. It was The emission was shifted to a single wavelength by changing the cluster size in the dendrimer.
【００４４】得られた錯体は、表２のとおり、原子吸光
スペクトル、赤外吸収スペクトル、およびマススペクト
ルにより同定した。The obtained complex was identified by atomic absorption spectrum, infrared absorption spectrum and mass spectrum as shown in Table 2.
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【発明の効果】以上詳しく説明した通り、この発明によ
って、発光材料や触媒材料等として有用な、金属クラス
ター内包フェニルアゾメチンデンドリマーが提供され
る。INDUSTRIAL APPLICABILITY As described in detail above, the present invention provides a phenylazomethine dendrimer containing a metal cluster, which is useful as a light emitting material, a catalyst material and the like.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4H049 VN03 VP02 VQ20 VR42 VS09 VT44 VU25 4J043 PA02 QB46 RA03 SB01 TA01 TB01 UA131 UA132 UB151 UB152 ZB25 ZB60 ─────────────────────────────────────────────────── ─── Continued front page F-term (reference) 4H049 VN03 VP02 VQ20 VR42 VS09 VT44 VU25 4J043 PA02 QB46 RA03 SB01 TA01 TB01 UA131 UA132 UB151 UB152 ZB25 ZB60
Claims (3)
ンデンドリマーに金属クラスターが内包されている錯体
物質であって、次の一般式 【化１】 （式中のＡは、フェニルアゾメチンデンドリマーの中核
分子基であり、次式 【化２】 の構造で表され、Ｒ1は、置換基を有していてもよい芳
香族基を示し、ｌはＲ1への結合数を示し；Ｂは、前記
Ａに対してｌ個のアゾメチン結合を形成する次式 【化３】 の構造で表わされ、Ｒ2は、同一または別異に置換基を
有していてもよい芳香族基を示し；Ｒは、末端基として
前記Ｂにアゾメチン結合する次式 【化４】 の構造で表わされ、Ｒ3は、同一または別異に置換基を
有していてもよい芳香族基を示し；ｎは、フェニルアゾ
メチンデンドリマーの前記Ｂの構造を介しての世代数を
示し；ｍは、フェニルアゾメチンデンドリマーの末端基
Ｒの数を表し、ｎ＝０の時はｍ＝ｌであり、ｎ≧１の時
はｍ＝２ｎｌであり；Ｄは金属クラスターを、ｋは金属
クラスターＤの数を各々表わしている）で示されること
を特徴とする金属クラスター内包フェニルアゾメチンデ
ンドリマー。1. A complex substance in which a metal cluster is included in a phenylazomethine dendrimer having a molecular dendritic structure, which is represented by the following general formula: (A in the formula is a core molecular group of the phenylazomethine dendrimer, and is represented by the following formula: R 1 represents an aromatic group which may have a substituent, 1 represents the number of bonds to R 1 , and B represents 1 azomethine bond to A above. The following formula is formed: Wherein R 2 represents an aromatic group which may be the same or different and which may have a substituent; R is a terminal group represented by the following formula: Wherein R 3 represents an aromatic group which may be the same or different and may have a substituent; n represents the number of generations of the phenylazomethine dendrimer through the structure of B. M is the number of terminal groups R of the phenylazomethine dendrimer, m = 1 when n = 0, m = 2nl when n ≧ 1; D is a metal cluster, k is a metal cluster A metal cluster-encapsulated phenylazomethine dendrimer, characterized in that each represents the number of D).
子またはそのイオンのクラスターであることを特徴とす
る請求項１の金属クラスター内包フェニルアゾメチンデ
ンドリマー。2. The metal cluster-encapsulating phenylazomethine dendrimer according to claim 1, wherein the metal cluster (D) is a cluster of semiconductor metal atoms or ions thereof.
アゾメチンデンドリマーを含有することを特徴とする発
光材料。3. A light emitting material comprising the phenylazomethine dendrimer containing a metal cluster according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002020785A JP3914057B2 (en) | 2002-01-29 | 2002-01-29 | Metal oxide cluster-encapsulated phenylazomethine dendrimer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002020785A JP3914057B2 (en) | 2002-01-29 | 2002-01-29 | Metal oxide cluster-encapsulated phenylazomethine dendrimer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003221442A true JP2003221442A (en) | 2003-08-05 |
| JP3914057B2 JP3914057B2 (en) | 2007-05-16 |
Family
ID=27744188
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002020785A Expired - Fee Related JP3914057B2 (en) | 2002-01-29 | 2002-01-29 | Metal oxide cluster-encapsulated phenylazomethine dendrimer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3914057B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076531A1 (en) * | 2003-02-27 | 2004-09-10 | Kanagawa Academy Of Science And Technology | Phenylazomethine dendrimer containing metal or metal cluster and method for preparation thereof |
| JP2004331850A (en) * | 2003-05-08 | 2004-11-25 | Kanagawa Acad Of Sci & Technol | Synthetic methods for phenylazomethine dendrimer and dendron derivative |
| WO2005032216A1 (en) * | 2003-09-26 | 2005-04-07 | Konica Minolta Holdings, Inc. | Compound of multi-branched structure, organic electroluminescent device, display, illuminating device, and method for producing compound of multi-branched structure |
| JP2006070100A (en) * | 2004-08-31 | 2006-03-16 | Keio Gijuku | Organic-organometallic compound-doped dendrimer |
| EP2153920A1 (en) * | 2007-05-09 | 2010-02-17 | National Institute for Materials Science | Metal nanoparticle, electrode using the same, and method for production of the same |
| JP2014513198A (en) * | 2010-12-30 | 2014-05-29 | インディアン インスティテュート オブ テクノロジー マドラス | Gold and silver quantum clusters and methods for preparing and using them |
| JP2014162909A (en) * | 2013-02-27 | 2014-09-08 | Tokyo Ohka Kogyo Co Ltd | Method for producing metal complex-supporting mesoporous material |
-
2002
- 2002-01-29 JP JP2002020785A patent/JP3914057B2/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076531A1 (en) * | 2003-02-27 | 2004-09-10 | Kanagawa Academy Of Science And Technology | Phenylazomethine dendrimer containing metal or metal cluster and method for preparation thereof |
| JPWO2004076531A1 (en) * | 2003-02-27 | 2006-06-01 | 財団法人神奈川科学技術アカデミー | Metal or metal cluster-containing phenylazomethine dendrimer and method for producing the same |
| JP4511125B2 (en) * | 2003-05-08 | 2010-07-28 | 財団法人神奈川科学技術アカデミー | Synthetic methods of phenylazomethine dendrimers and dendron derivatives |
| JP2004331850A (en) * | 2003-05-08 | 2004-11-25 | Kanagawa Acad Of Sci & Technol | Synthetic methods for phenylazomethine dendrimer and dendron derivative |
| WO2005032216A1 (en) * | 2003-09-26 | 2005-04-07 | Konica Minolta Holdings, Inc. | Compound of multi-branched structure, organic electroluminescent device, display, illuminating device, and method for producing compound of multi-branched structure |
| JP5098172B2 (en) * | 2003-09-26 | 2012-12-12 | コニカミノルタホールディングス株式会社 | ORGANIC ELECTROLUMINESCENCE ELEMENT, DISPLAY DEVICE, LIGHTING DEVICE, AND METHOD FOR PRODUCING LIGHT EMITTING MATERIAL INCLUDING MULTI-BRANCHED STRUCTURE COMPOUND |
| JP2006070100A (en) * | 2004-08-31 | 2006-03-16 | Keio Gijuku | Organic-organometallic compound-doped dendrimer |
| JP4604220B2 (en) * | 2004-08-31 | 2011-01-05 | 学校法人慶應義塾 | Organic and organometallic compound-containing dendrimers |
| EP2153920A1 (en) * | 2007-05-09 | 2010-02-17 | National Institute for Materials Science | Metal nanoparticle, electrode using the same, and method for production of the same |
| EP2153920A4 (en) * | 2007-05-09 | 2014-06-04 | Nat Inst For Materials Science | Metal nanoparticle, electrode using the same, and method for production of the same |
| JP2014513198A (en) * | 2010-12-30 | 2014-05-29 | インディアン インスティテュート オブ テクノロジー マドラス | Gold and silver quantum clusters and methods for preparing and using them |
| US8999717B2 (en) | 2010-12-30 | 2015-04-07 | Indian Institute Of Technology Madras | Gold and silver quantum clusters in molecular containers and methods for their preparation and use |
| US9494517B2 (en) | 2010-12-30 | 2016-11-15 | Indian Institute Of Technology Madras | Gold and silver quantum clusters in molecular containers and methods for their preparation and use |
| JP2014162909A (en) * | 2013-02-27 | 2014-09-08 | Tokyo Ohka Kogyo Co Ltd | Method for producing metal complex-supporting mesoporous material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3914057B2 (en) | 2007-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | Strategies toward efficient blue perovskite light‐emitting diodes | |
| Li et al. | Reconstructing the surface of gold nanoclusters by cadmium doping | |
| Mu et al. | Facile one-pot synthesis of L-proline-stabilized fluorescent gold nanoclusters and its application as sensing probes for serum iron | |
| JP4756069B2 (en) | Etching composition | |
| JP5530695B2 (en) | Organometallic complex, light emitting element, and electronic device | |
| JP5281270B2 (en) | Iridium complex compound, organic electroluminescence device using the same, and use thereof | |
| Shahedi et al. | Synthesis of ZnQ 2, CaQ 2, and CdQ 2 for application in OLED: optical, thermal, and electrical characterizations | |
| Li et al. | Atomically precise copper cluster with intensely near-infrared luminescence and its mechanism | |
| JP2009507996A (en) | Atomic quantum cluster, method for producing the same, and method for using the same | |
| Capel Berdiell et al. | Iron (II) Complexes of 2, 4-Dipyrazolyl-1, 3, 5-triazine Derivatives The Influence of Ligand Geometry on Metal Ion Spin State | |
| Xu et al. | Entrapped planar trimetallic carbide in a fullerene cage: synthesis, isolation, and spectroscopic studies of Lu3C2@ C88 | |
| JP2003221442A (en) | Metal cluster-containing phenylazomethine dendrimer | |
| Kobayashi et al. | An adjacent dibenzotetraazaporphyrin: a structural intermediate between tetraazaporphyrin and phthalocyanine | |
| Fan et al. | Syntheses and structures of blue-luminescent mercury (II) complexes with 2, 6-Bis (imino) pyridyl ligands | |
| Zhan et al. | Facile synthesis of a terephthalic acid-based organic fluorophore with strong and color-tunable emission in both solution and solid states for LED applications | |
| Zhu et al. | Surface engineering of gold nanoclusters protected with 11-mercaptoundecanoic acid for photoluminescence sensing | |
| JP5757615B2 (en) | Organic / metal hybrid polymer comprising a metal having a coordination number of 4 and a bisphenanthroline derivative, a ligand thereof, and a production method thereof | |
| Yi et al. | Superatom‐in‐Superatom Nanoclusters: Synthesis, Structure, and Photoluminescence | |
| JP3790149B2 (en) | Metal nano-sized particles and manufacturing method thereof | |
| JPWO2009031507A1 (en) | Organic switching element and manufacturing method thereof | |
| Amini et al. | Structure and optical properties of new lead (II) coordination polymers and PbO nanoparticles core of polymer | |
| JP3687791B2 (en) | Novel rare earth complexes with circularly polarized light emission | |
| He et al. | Dispersion-assisted tunable fluorescence from carbon dots | |
| JPWO2004076531A1 (en) | Metal or metal cluster-containing phenylazomethine dendrimer and method for producing the same | |
| JP3977649B2 (en) | Phenylazomethine dendron complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20041112 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20050623 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20050705 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20050905 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20051108 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20060110 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070123 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20070201 |
|
| R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100209 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110209 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120209 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120209 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130209 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140209 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140209 Year of fee payment: 7 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |